EP2781350A1 - Élément composé ignifuge - Google Patents

Élément composé ignifuge Download PDF

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Publication number
EP2781350A1
EP2781350A1 EP12850042.8A EP12850042A EP2781350A1 EP 2781350 A1 EP2781350 A1 EP 2781350A1 EP 12850042 A EP12850042 A EP 12850042A EP 2781350 A1 EP2781350 A1 EP 2781350A1
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EP
European Patent Office
Prior art keywords
flame
composite member
resistant composite
resin composition
silicone resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12850042.8A
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German (de)
English (en)
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EP2781350A4 (fr
EP2781350B1 (fr
Inventor
Kohei Doi
Kunio Nagasaki
Yusuke Sugino
Takafumi Hida
Yusuke Nakayama
Keisuke Hirano
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of EP2781350A4 publication Critical patent/EP2781350A4/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/05—Forming flame retardant coatings or fire resistant coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V25/00—Safety devices structurally associated with lighting devices
    • F21V25/12—Flameproof or explosion-proof arrangements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a flame-resistant composite member, more particularly to a flame-resistant composite member obtained by forming as a film a silicone resin composition containing at least an inorganic oxide particle-containing condensation-reactive silicone resin on a base material, and an illumination apparatus using the flame-resistant composite member.
  • Halogen-based flame resistants are conventionally broadly used as flame resistants to make coating compositions flame-resistant (see, for example, Patent Literature 1).
  • this method since having the problem of dioxins and flons generated from halogenated flame-resistants, cannot be said to be preferable on the environmental protection.
  • Inorganic flame resistants such as aluminum hydroxide are also used as flame resistants to make coating compositions flame-resistant.
  • aluminum hydroxide has the problem of decreasing physical properties, including the water resistance, of coating materials and base materials to which the coating materials have been applied.
  • Glass fiber sheets on which an inorganic coating agent has been applied are conventionally known as railway rolling stock illumination covers.
  • glass fiber sheets which have been coated with a common inorganic coating agent or which are impregnated with the inorganic coating agent, in the case where the binder contains an organic component have the problem of low nonflammability; and those, in the case where the binder is an inorganic component, have drawbacks of low flexibility and easy cracking.
  • Patent Literature 2 discloses a light diffusion sheet including at least one sheet of a glass fiber woven cloth and a pair of resin layers interposing the glass fiber woven cloth, wherein the resin layers are constituted of a thermosetting resin or photocurable resin such as a vinyl ester.
  • Patent Literature 3 discloses a glass fiber sheet having at least one sheet of a glass fiber woven cloth, resin-coated layers composed of a thermosetting resin formed by being impregnated and solidified in the glass fiber woven cloth, and a bead layer on at least one surface of the resin-coated layers.
  • either of these light diffusion sheets exhibits insufficient nonflammability and low flexibility.
  • the present invention provides a flame-resistant composite member having a film formed of a silicone resin composition (C) containing at least an inorganic oxide particle-containing condensation-reactive silicone resin on at least one surface of a base material.
  • condensation-reactive silicone resin comprising a crosslinked structural body wherein an inorganic oxide particle dispersed in a polysiloxane resin having a condensation-reactive group and the polysiloxane resin are crosslinked through a chemical bond.
  • condensation-reactive silicone resin (A) as the polysiloxane resin having a condensation-reactive group, there may be used (i) a condensation-reactive group-containing polysilsesquioxane wherein a basic structural unit thereof is a T unit, or (ii) the condensation-reactive group-containing polysilsesquioxane wherein a basic structural unit thereof is a T unit and also a condensation-reactive group-containing polysiloxane wherein basic structural units thereof are a D unit and a T unit and/or a polysiloxane resin having a silanol group.
  • the silicone resin composition (C) containing at least the inorganic oxide particle-containing condensation-reactive silicone resin may contain: a condensation-reactive silicone resin (A) comprising a crosslinked structural body wherein an inorganic oxide particle dispersed in a polysiloxane resin having a condensation-reactive group and the polysiloxane resin are crosslinked through a chemical bond; and an inorganic particle (B).
  • the inorganic particle (B) may be at least one inorganic particle selected from the group consisting of glass frits, silica particles, alumina particles, aluminum hydroxide particles, magnesium hydroxide particles, tin oxide particles and clay mineral particles.
  • the deformation point of the glass frit as the inorganic particle (B) may be not less than 300°C and not more than 700°C.
  • the glass frit as the inorganic particle (B) may be a glass frit formed of at least one component selected from silicic acid, boric acid, borosilicic acid, aluminum oxide, calcium oxide, sodium oxide, lithium oxide and phosphorus oxide.
  • the glass frit as the inorganic particle (B) is especially preferably a glass frit formed of at least a component containing phosphorus oxide.
  • the average particle diameter of the glass frit as the inorganic particle (B) is, for example, 0.1 ⁇ m to 1,000 ⁇ m.
  • the content of the inorganic particle (B) is, for example, 0.1 to 500 parts by weight with respect to 100 parts by weight of a condensation-reactive silicone resin (A).
  • the base material may be a sheet-like or plate-like plastic-based base material.
  • the thickness of a flame-resistant composite member is, for example, 50 to 6,000 ⁇ m.
  • the thickness of a film formed of the silicone resin composition (C) is, for example, 5 to 1,000 ⁇ m.
  • the flame-resistant composite member preferably has a property of not igniting or carbonizing in the combustion test of the railway rolling stock material combustion test.
  • the flame-resistant composite member preferably has the nonflammability in the combustion test of the railway rolling stock material combustion test.
  • the flame-resistant composite member in the cone calorimeter test of the railway rolling stock material combustion test, preferably further has a total amount of heat generated per 10 min of not more than 30 MJ/m 2 , a maximum heat generation rate of not more than 300 kW/m 2 , and an ignition time of not less than 60 sec.
  • the flame-resistant composite member is used, for example, as transport machinery interior members, building material members, display members, household appliance members or electronic circuit members.
  • the transport machinery interior members include, for example, illumination covers.
  • the present invention also provides an illumination apparatus using the flame-resistant composite member, the illumination apparatus having, at least, a light source to generate light used for illumination, and an illumination cover installed so as to cover the light source and having the flame-resistant composite member, wherein light from the light source is transmitted through the flame-resistant composite member and emitted.
  • the flame-resistant composite member according to the present invention since having a film formed of a silicone resin composition containing an inorganic oxide particle-containing condensation-reactive silicone resin on a base material, is very excellent in flame resistance, and even if the base material is flammable, does not spread fire in flame contact, and preferably does not ignite or carbonize.
  • the flame-resistant composite member having a film formed of a silicone resin composition containing a specific condensation-reactive silicone resin and an inorganic particle on a base material is more improved in the strength of the film, exhibits remarkably high flame resistance, and even if the thickness of the base material is relatively thin, does not spread fire in flame contact and further does not ignite or carbonize.
  • the flame-resistant composite member according to the present invention is useful particularly as interior members of transport machinery such as railway rolling stock, air carriers, automobiles, ships, elevators and escalators, building material members, display members, household appliance members and electronic circuit members.
  • the flame-resistant composite member can suitably be utilized particularly as illumination covers of illumination apparatuses.
  • the flame-resistant composite member according to the present invention has a film (an inorganic oxide particle-containing silicone resin film) formed of a silicone resin composition (C) containing at least an inorganic oxide particle-containing condensation-reactive silicone resin on at least one surface of a base material.
  • FIG. 1 is a schematic cross-sectional diagram showing one example of the flame-resistant composite member according to the present invention.
  • the flame-resistant composite member 3 has a film (coated layer) 2 formed of an inorganic oxide particle-containing condensation-reactive silicone resin on one surface of a base material 1.
  • the film may be formed on both surfaces of the base material 1.
  • a base material is not especially limited as long as being capable of becoming an object to be imparted with or improved in the flame resistance, but is preferably sheet-like or plate-like.
  • a layer material composed of a pressure-sensitive adhesive agent is not included in the base material in the present invention.
  • Base materials usable are suitable thin sheet bodies, for example, plastic-based base materials such as plastic sheets and plates; rubber-based base materials such as rubber sheets; foamed bodies such as foamed sheets; paper-based base materials such as paper; fiber-based base materials (excluding glass fiber base materials) such as cloths, nonwoven fabrics and nets; and laminated bodies thereof [for example, laminated bodies of a plastic-based base material and another base material and a laminated body of plastic sheets or plastic plates].
  • plastic-based base materials such as plastic sheets and plates (including laminated bodies containing at least a plastic-based base material) can suitably be used.
  • Materials for such plastic sheets or the like include thermoplastic resins and thermosetting resins.
  • the thermoplastic resins include olefin-based resins using ⁇ -olefins as monomers such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymers and ethylene-vinyl acetate copolymers (EVA); polyester-based resins such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBT); polyvinyl chlorides (PVC); vinyl acetate-based resins; styrene-based resins such as polystyrenes, ABS resins and AS resins; acryl resins; polyacrylonitriles; polyphenylene sulfides (PPS); amide-based resins such
  • olefin-based resins such as polyethylenes and polypropylenes
  • polycarbonate resins especially preferable is polycarbonate resins.
  • plastics having been subjected to a flame-resistant treatment may preferably be used.
  • the flame-resistant treatment method is not especially limited, but includes the addition of an organic flame resistant or an inorganic flame resistant, and the addition of a glass fiber or a filler to improve the plastic strength.
  • the organic flame resistant includes fluorine-based compounds, chlorine-based compounds, bromine-based compounds, phosphorus-based compounds, silicone-based compounds, sulfur-based flame resistants
  • the inorganic flame resistant includes metal hydroxides such as aluminum hydroxide and magnesium hydroxide, boron-based compounds, phosphorus-based compounds, antimony-based compounds, and sulfur-based flame resistants.
  • one surface thereof on the side to form an inorganic oxide particle-containing silicone resin film on is preferably subjected to no peeling treatment from the viewpoint of the adherence.
  • the thickness of a base material can suitably be selected according to applications and the like, but the upper limit is usually 5,000 ⁇ m, preferably 4,000 ⁇ m, and still more preferably 3,000 ⁇ m: and the lower limit is, for example, 45 ⁇ m, preferably 80 ⁇ m, still more preferably 100 ⁇ m, and especially preferably 150 ⁇ m.
  • a primer layer directly contacting with both of the film formed of the silicone resin composition (C), and the base material.
  • a compound used for forming the primer layer suffices if being a component (including a component to develop the adhesivity by curing or reaction) having the adhesivity with both of the film formed of the silicone resin composition (C), and the base material; examples thereof include silane-based coupling agents (including partially hydrolytic condensates) and (meth)acryloyl group-containing organic compounds, and are not especially limited; but silane-based coupling agents are preferable from the viewpoint that the surface hardly carbonizes in combustion.
  • silane-based coupling agent examples include ones having a reactive functional group such as an amino group, a vinyl group, an epoxy group, a mercapto group, a chlorine group or a (meth)acryloyl group, and a hydrolyzable alkoxysilyl group in the same molecule, and are not especially limited; but amino group-containing silane coupling agents are preferable from the viewpoint of the anchoring property with a base material.
  • amino group-containing silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-dimethylaminopropy(triethoxy)silane, 3-dimethylaminopropyl(trimethoxy)silane, 3-diethylaminopropyl(triethoxy)silane, 3-diethylaminopropyl(trimethoxy)silane, 2-dimethylaminoethyl(triethoxy)silane, 2-dimethylaminoethyl(trimethoxy)silane, 3-dimethylaminopropyl(diethoxy)methylsilane, 3-dibutylaminopropyl(triethoxy)silane, aminophenyltrimethoxysilane, aminophenyltriethoxysilane, 3-(N-methylamino)propyltrimethoxysilane and 3-(N-methylmethylamin
  • a primer treatment can be carried out by applying a composition containing the above-mentioned compound (adhesive component) on the base material surface by using a method such as coating, dip coating or spray coating.
  • a method such as coating, dip coating or spray coating.
  • the incorporation of a solvent to dissolve a base material in the composition roughens the base material surface and can exhibit the anchoring effect.
  • a base material On at least one surface of a base material, there may be provided, in addition to the above-mentioned primer layer (easily adhesive layer), a light diffusion layer, an antireflection layer, an ultraviolet absorption layer, a heat barrier layer, a heat insulation layer and the like, in the range of not impairing the flame resistance.
  • primer layer adhesive layer
  • a light diffusion layer an antireflection layer, an ultraviolet absorption layer, a heat barrier layer, a heat insulation layer and the like, in the range of not impairing the flame resistance.
  • a “condensation-reactive silicone resin” of an "inorganic oxide particle-containing condensation-reactive silicone resin” in the present invention is not especially limited as long as being a silicone resin (polysiloxane resin) having a condensation-reactive group; and examples thereof include condensation-reactive group-containing polysiloxanes wherein basic structural units thereof are a D unit and a T unit (hereinafter, referred to as "D-T unit condensation-reactive group-containing polysiloxane” in some cases), condensation-reactive group-containing polysilsesquioxanes wherein a basic structural unit thereof is a T unit (hereinafter, referred to as "condensation-reactive group-containing polysilsesquioxane” in some cases), and condensation-reactive group-containing polysiloxanes wherein basic structural units thereof are an M unit and a Q unit. These may be used singly or in combinations of not less than two.
  • condensation-reactive silicone resins from the viewpoint of being capable of imparting the flexibility to a composite member, preferable are a D-T unit condensation-reactive group-containing polysiloxane, a condensation-reactive group-containing polysilsesquioxane, and a combination of a D-T unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane.
  • a condensation-reactive group-containing polysilsesquioxane or a combination of a D-T unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane.
  • the condensation-reactive group includes silanol groups, alkoxysilyl groups (for example, C 1-6 alkoxysilyl groups), cycloalkyloxysilyl groups (for example, C 3-6 cycloalkyloxysilyl groups), and aryloxysilyl groups (for example, C 6-10 aryloxysilyl groups).
  • silanol groups for example, alkoxysilyl groups, cycloalkyloxysilyl groups, and aryloxysilylgroups
  • silanol groups and alkoxysilyl groups for example, C 1-6 alkoxysilyl groups
  • cycloalkyloxysilyl groups for example, C 3-6 cycloalkyloxysilyl groups
  • aryloxysilyl groups for example, C 6-10 aryloxysilyl groups.
  • a D-T unit condensation-reactive group-containing polysiloxane specifically contains as basic structural units a D unit represented by the following formula (1) and a T unit represented by the following formula (2).
  • R 1 are identical or different, and each represent a monovalent hydrocarbon group selected from saturated hydrocarbon groups and aromatic hydrocarbon groups.
  • R 2 represents a monovalent hydrocarbon group selected from saturated hydrocarbon groups and aromatic hydrocarbon groups.
  • Examples of the saturated hydrocarbon group in the above R 1 and R 2 include straight-chain or branched-chain alkyl groups having 1 to 6 carbon atoms such as a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl groups; and cycloalkyl groups having 3 to 6 carbon atoms such as a cyclopentyl and cyclohexyl groups.
  • Examples of the aromatic hydrocarbon group in the above R 1 and R 2 include aryl groups having 6 to 10 carbon atoms such as a phenyl and naphthyl groups.
  • R 1 and R 2 are preferably each an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group.
  • D units represented by the formula (1) may be identical or different in a D-T unit condensation-reactive group-containing polysiloxane, but are preferably identical.
  • T units represented by the formula (2) may be identical or different in a D-T unit condensation-reactive group-containing polysiloxane, but are preferably identical.
  • a D-T unit condensation-reactive group-containing polysiloxane is a partial condensate of corresponding silicone monomers [for example, a partial condensate of a bifunctional silicone monomer such as a dialkyl(or aryl)dialkoxysilane, and a trifunctional silicone monomer such as an alkyl(or aryl)trialkoxysilane], and contains a D unit, a T unit and a group represented by the following formula (3): -OR 3 (3) in the constituting units.
  • the group represented by the formula (3) bonds to a silicon atom, and is present at the molecular terminal.
  • R 3 represents a monovalent hydrocarbon group selected from saturated hydrocarbon groups and aromatic hydrocarbon groups.
  • the saturated hydrocarbon group or the aromatic hydrocarbon group includes the same as the saturated hydrocarbon group or the aromatic hydrocarbon group in R 1 in the above formula (1).
  • R 3 is preferably a saturated hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and especially preferably a methyl group or an ethyl group.
  • Examples of such a D-T unit condensation-reactive group-containing polysiloxane include alkoxysilyl group-(for example, C 1-6 alkoxysilyl group-)containing polymethylsiloxanes, alkoxysilyl group- (for example, C 1-6 alkoxysilyl group-)containing polymethylphenylsiloxanes, alkoxysilyl group- (for example, C 1-6 alkoxysilyl group-)containing polyphenylsiloxanes.
  • These D-T unit alkoxysilyl group-containing polysiloxanes may be used singly or in combinations of not less than two.
  • D-T unit condensation-reactive group-containing polysiloxane preferable are C 1-6 alkoxysilyl group-containing polysiloxanes; more preferable are methoxysilyl group-containing polysiloxanes or ethoxysilyl group-containing polysiloxanes; and especially preferable are methoxysilyl group-containing polymethylsiloxanes or ethoxysilyl group-containing polymethylsiloxanes.
  • the upper limit is, for example, 30 wt%, and preferably 25 wt%; and the lower limit is, for example, 8 wt%, preferably 10 wt%, and more preferably 12 wt%.
  • the content of the condensation-reactive group can be determined from a proportion of a weight loss in TGA'(using a differential weight loss measurement instrument) of the polysiloxane when the polysiloxane is heated from room temperature to 300°C.
  • the upper limit is, for example, 6,000, preferably 5,500, and more preferably 5,300; and the lower limit is, for example, 800, preferably 1,000, and more preferably 1,200.
  • D-T unit condensation-reactive group-containing polysiloxane there can also be used commercially available products (D-T unit alkoxysilyl group-containing polysiloxanes) such as "X-40-9246" and "X-40-9250” by trade names (the above-mentioned are made by Shin-Etsu Chemical Co., Ltd.).
  • the condensation-reactive group-containing polysilsesquioxane specifically contains a T unit represented by the above formula (2) as a basic structural unit.
  • the T units represented by the formula (2) may be identical or different in the condensation-reactive group-containing polysilsesquioxane, but are preferably identical.
  • a condensation-reactive group-containing polysilsesquioxane is a partial condensate of a corresponding silicone monomer [for example, a partial condensate of a trifunctional silicone monomer such as an alkyl(or aryl)trialkoxysilane], and contains a T unit and a group represented by the following formula (4): -OR 4 (4) in the constituting units.
  • the group represented by the formula (4) bonds to a silicon atom, and is present at the molecular terminal.
  • the R 4 represents a monovalent hydrocarbon group selected from saturated hydrocarbon groups and aromatic hydrocarbon groups.
  • the saturated hydrocarbon group or the aromatic hydrocarbon group includes the same as the saturated hydrocarbon group or the aromatic hydrocarbon group in R 1 in the above formula (1).
  • R 4 is preferably a saturated hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and especially preferably a methyl group or an ethyl group.
  • a condensation-reactive group-containing polysilsesquioxane may be of any of random type, ladder type, cage type and the like, but is most preferably of random type from the viewpoint of the flexibility. These condensation-reactive group-containing polysilsesquioxanes may be used singly or in combinations of not less than two.
  • condensation-reactive group-containing polysilsesquioxanes preferable are C 1-6 alkoxysilyl group-containing polysilsesquioxanes; more preferable are methoxysilyl group-containing polysilsesquioxanes or ethoxysilyl group-containing polysilsesquioxanes; and especially preferable are methoxysilyl group-containing polymethylsilsesquioxanes or ethoxysilyl group-containing polymethylsilsesquioxanes.
  • the upper limit is, for example, 50 wt%, preferably 48 wt%, and more preferably 46 wt%; and the lower limit is, for example, 10 wt%, preferably 15 wt%, and more preferably 20 wt%.
  • the content of the condensation-reactive group can be determined from a proportion of a weight loss in TGA (using a differential weight loss measurement instrument) of the polysilsesquioxane when the polysilsesquioxane is heated from room temperature to 300°C.
  • the upper limit is, for example, 6,000, preferably 3,500, and more preferably 3,000; and the lower limit is, for example, 200, preferably 300, and more preferably 400.
  • condensation-reactive group-containing polysilsesquioxane there can also be used commercially available products (alkoxysilyl group-containing polysilsesquioxanes) such as "KC-89", “KR-500” and “X-40-9225” by trade names (the above-mentioned are made by Shin-Etsu Chemical Co., Ltd.).
  • polysiloxane compounds having a reactive silanol group in the molecule such as "X-21-3153" and “X-21-5841” by trade names (the above-mentioned are made by Shin-Etsu Chemical Co., Ltd.).
  • the proportion of the total amount of a D-T unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane in the whole of the polysiloxane compound is preferably not less than 50 wt%, more preferably not less than 70 wt%, and especially preferably not less than 90 wt%.
  • the polysiloxane resin is a polysiloxane resin having an alkoxysilyl group and/or a silanol group in the molecule (molecular terminal), and having a total content of these groups (the alkoxysilyl group and the silanol group) of 8 to 48 wt%; and the polysiloxane resin is preferably crosslinked with the inorganic oxide particle through a chemical bond.
  • the upper limit of the total content of the alkoxysilyl group and the silanol group is more preferably 30 wt%; and the lower limit is more preferably 10 wt%.
  • condensation-reactive silicone resin it is preferable particularly from the viewpoint of the flexibility, the strength, the nonflammability and the like that a condensation-reactive group-containing polysilsesquioxane is used, or a D-T unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane are concurrently used.
  • the upper limit is, for example, 4.9, preferably 3, and more preferably 2; and the lower limit is, for example, 0, and preferably 0.02; but in the case of further imparting the flexibility, the upper limit is, for example, 100. If the ratio of a D-T unit condensation-reactive group-containing polysiloxane is too high, since the organic group content increases, there arise some cases where the silicone resin is liable to ignite and spread fire.
  • the inorganic oxide particle-containing condensation-reactive silicone resin it is preferable from the viewpoint of the heat resistance and the strength that a crosslinked structural body is used in which a condensation-reactive silicone resin is crosslinked with an inorganic oxide particle through a chemical bond.
  • a condensation-reactive silicone resin (A) comprising a crosslinked structural body wherein an inorganic oxide particle dispersed in a polysiloxane resin having a condensation-reactive group and the polysiloxane resin are crosslinked through a chemical bond.
  • the condensation-reactive silicone resin (A) will be described.
  • a polysiloxane resin having a condensation-reactive group As a polysiloxane resin having a condensation-reactive group, the above-mentioned ones can be used. Among those, preferable is a condensation-reactive group-containing polysilsesquioxane, or a combination of a D-T unit condensation-reactive group-containing polysiloxane and a condensation-reactive group-containing polysilsesquioxane.
  • an inorganic oxide particle suffices if having a reactive functional group on the particle surface, and examples thereof include silica (SiO 2 or SiO), alumina (Al 2 O 3 ), glass frits, antimony-doped tin oxide (ATO), titanium oxide (titania, TiO 2 ), and zirconia (ZrO 2 ).
  • the inorganic oxide particle may be a composite inorganic oxide particle composed of not less than two inorganic oxides. Among these, silica is especially preferable.
  • the inorganic oxide particle may be used singly or in combinations of not less than two.
  • Examples of the reactive functional group include a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, an amino group, a mercapto group, a vinyl-type unsaturated group, a halogen atom, and an isocyanurate group.
  • a hydroxyl group is preferable.
  • the hydroxyl group on the silica particle surface is present as a silanol group.
  • the upper limit is, for example, 500 ⁇ m, preferably 100 ⁇ m, more preferably 10 ⁇ m, and especially preferably 1 ⁇ m; and the lower limit is, for example, 1 nm.
  • the average particle diameter can be measured by a dynamic light scattering method or the like.
  • the size distribution of an inorganic oxide particle is desirably narrower, and the inorganic oxide particle is also desirably in a monodisperse state of being dispersed while being in the state of the primary particle diameter.
  • the surface potential of an inorganic oxide particle is preferably in an acidic range (for example, pH 2 to 5, preferably pH 2 to 4). The surface potential suffices if being such a surface potential in the reaction with a polysiloxane resin.
  • the inorganic oxide particle in a colloidal state is preferably used.
  • the colloidal inorganic oxide particle include colloidal silica, colloidal alumina (alumina sol), and colloidal tin oxide (tin oxide water dispersion).
  • colloidal silica examples include colloids of microparticles (average particle diameter is, for example, 5 to 1,000 nm, and preferably 10 to 100 nm) of silicon dioxide (anhydrous silicic acid) as described in Japanese Patent Laid-Open No. 53-112732 and Japanese Patent Publication Nos. 57-9051 and 57-51653 , and the like.
  • the colloidal silica can contain, for example, alumina and sodium aluminate, and as required, also can contain a stabilizer such as an inorganic base (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia) and an organic base (for example, a tetramethylammonium).
  • a stabilizer such as an inorganic base (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia) and an organic base (for example, a tetramethylammonium).
  • Such a colloidal silica is not especially limited, and can be produced by a well-known sol-gel method, specifically for example, a sol-gel method described in Werner Stober et al, J. Colloid and Interface Sci., 26, 62-69 (1968 ), Rickey D. Badley et al, Langmuir 6, 792-801 (1990 ), Journal of Japan Society of Color Material, 61 [9] 488-493 (1988 ), or the like.
  • the colloidal silica is preferably in a bare state of being subjected to no surface treatment.
  • the colloidal silica has a silanol group present as a surface functional group.
  • colloidal silica commercially available products can be used, and specific examples thereof include “Snowtex-XL”, “Snowtex-YL”, “Snowtex-ZL", “PST-2", "Snowtex-20”, “Snowtex-30”, “Snowtex-C” "Snowtex-O”, "Snowtex-OS”, “Snowtex-OL” and “Snowtex-50” by trade names (the above-mentioned are made by Nissan Chemical Industries, Ltd.), and “Adelite AT-30", “Adelite AT-40” and “Adelite AT-50” by trade names (the above-mentioned are made by Nippon Aerosil Co., Ltd.).
  • especially preferable are “Snowtex-O", “Snowtex-OS”, “Snowtex-OL” by trade names, and the like.
  • colloidal inorganic particles other than the above-mentioned colloidal silicas commercially available products can be used, and specific examples thereof include an alumina sol (hydrosol) such as "Alumina Sol 100", “Alumina Sol 200" and “Alumina Sol 520" by trade names (the above-mentioned are made by Nissan Chemical Industries, Ltd.), a titania sol (hydrosol) such as "TTO-W-5" by trade name (made by Ishihara Sangyo Kaisha Ltd.) and "TS-020" by trade name (made by Tayca Corp.), and tin oxide water dispersions such as "SN-100D” and "SN-100S” by trade names (the above-mentioned are made by Ishihara Sangyo Kaisha Ltd.).
  • alumina sol such as "Alumina Sol 100", “Alumina Sol 200" and “Alumina Sol 520" by trade names (the above-mentioned are made by Nissan Chemical Industries, Ltd.)
  • the inorganic oxide particle is a colloidal silica whose primary particle diameter is in the range of 1 nm to 500 ⁇ m and whose surface potential is in the range of pH 2 to 5, and the silanol group of the colloidal silica surface chemically bonds with a polysiloxane resin to crosslink the polysiloxane resin.
  • the content (or the content of inorganic oxide particle in a film) of an inorganic oxide particle in the inorganic oxide particle-containing condensation-reactive silicone resin can suitably be selected, but the upper limit is, for example, 30 wt%, preferably 20 wt%, and more preferably 15 wt%; and the lower limit is, for example, 1 wt%, preferably 2 wt%, and more preferably 3 wt%. If the content of an inorganic oxide particle is too low, the mechanical strength of a film is liable to decrease; and if the content of an inorganic oxide particle is too high, the film is liable to become brittle.
  • the inorganic oxide particle-containing condensation-reactive silicone resin can be produced, for example, by allowing the inorganic oxide particle and the polysiloxane resin having a condensation-reactive group (preferably, the condensation-reactive group-containing polysilsesquioxane, or the D-T unit condensation-reactive group-containing polysiloxane and the condensation-reactive group-containing polysilsesquioxane, or these and the polysiloxane resin having a silanol group) to react in a solvent, preferably in the presence of an acid.
  • the polysiloxane resin has a functional group reactive with a reactive functional group on the particle surface of the inorganic oxide particle.
  • the reactive functional group on the particle surface of the inorganic oxide particle is a silanol group
  • the condensation-reactive group reacts with the silanol group to form a crosslinked structure.
  • the solvent includes water, alcohols such as methanol, ethanol, 2-propanol and 2-methoxyethanol, and mixed liquids thereof.
  • mixed solvents of water and an alcohol are preferable, and more preferable are a mixed solvent of water and 2-propanol and a mixed solvent of water and 2-propanol and 2-methoxyethanol.
  • the acid examples include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; and organic acids such as acetic acid and p-toluenesulfonic acid. Among these, inorganic acids are preferable, and nitric acid is especially preferable. These acids can be used as an aqueous solution.
  • the amount of an acid used can be in an amount capable of regulating the pH of a reaction system at about 2 to 5 (preferably 2 to 4).
  • the reaction method is not especially limited, and may be any of, for example, (i) a method in which a mixed liquid of a polysiloxane resin and a solvent is added to a mixed liquid of an inorganic oxide particle and a solvent, (ii) a method in which a mixed liquid of an inorganic oxide particle and a solvent is added to a mixed liquid of a polysiloxane resin and a solvent, and (iii) a method in which a mixed liquid of an inorganic oxide particle and a solvent and a mixed liquid of a polysiloxane resin and a solvent are both added to a solvent.
  • an inorganic oxide particle and a mixture of the D-T unit condensation-reactive group-containing polysiloxane and the condensation-reactive group-containing polysilsesquioxane may be allowed to react; or, the D-T unit condensation-reactive group-containing polysiloxane may be first allowed to react with the inorganic oxide particle, and the condensation-reactive group-containing polysilsesquioxane may be then allowed to react; or, the condensation-reactive group-containing polysilsesquioxane may be first allowed to react with the inorganic oxide particle, and the D-T unit condensation-reactive group-containing polysiloxane may be then allowed to react.
  • a condensation-reactive group- silyl group-containing polysilsesquioxane is first allowed to react with an inorganic oxide particle, and a D-T unit condensation-reactive group-containing polysiloxane and/or a polysiloxane resin having a silanol group is then allowed to react, and in the case of coating at least one surface of a base material with the silicone resin to thereby provide a film composed of the silicone resin, the flexibility of the film is greatly improved.
  • the upper limit of the reaction temperature is, for example, 150°C, and preferably 130°C; and the lower limit is, for example, 40°C, and preferably 50°C.
  • the upper limit of the reaction time is, for example, 24 hours, and preferably 12 hours; and the lower limit is, for example, 0.2 hours, and preferably 0.5 hours.
  • a silicone resin composition (C) containing at least an inorganic oxide particle-containing condensation-reactive silicone resin can be obtained.
  • the silicone resin composition (C) containing at least an inorganic oxide particle-containing condensation-reactive silicone resin may contain: a condensation-reactive silicone resin (A) comprising a crosslinked structural body wherein an inorganic oxide particle dispersed in the polysiloxane resin having a condensation-reactive group and the polysiloxane resin are crosslinked through a chemical bond; and an inorganic particle (B).
  • a condensation-reactive silicone resin (A) comprising a crosslinked structural body wherein an inorganic oxide particle dispersed in the polysiloxane resin having a condensation-reactive group and the polysiloxane resin are crosslinked through a chemical bond
  • an inorganic particle (B) an inorganic particle
  • the inorganic particle (B) is not especially limited, and examples thereof include silica particles, alumina particles, aluminum hydroxide particles, titanium oxide particles, magnesium oxide particles, magnesium hydroxide particles, tin oxide particles, zirconia particles, clay mineral particles (talc, zeolite and the like), and glass frits. These can be used singly or in combinations of not less than two.
  • the inorganic particle (B) is in the state of not being chemically bonded with the polysiloxane resin having a condensation-reactive group.
  • silica particles, alumina particles, aluminum hydroxide particles, magnesium hydroxide particles, and glass frits are preferable, from the viewpoint of providing a high flame-resistant effect in a small amount thereof.
  • Silica particles and glass frits are more preferable from the viewpoint of further providing the transparency; and glass frits are especially preferable particularly from the viewpoint of providing a heat generation suppressing effect in the cone calorimeter test.
  • silica particle examples include dry silica particles such as fumed silica particles and fused silica particles, wet silica particles, silica gel particles, and colloidal silica particles.
  • silica particles fumed silica particles such as Aerosil are preferable, and hydrophobic fumed silica particles are especially preferable.
  • the deformation point of the glass frit is preferably 300 to 700°C, more preferably 300 to 650°C, and still more preferably 300 to 600°C.
  • the effect of suppressing the amount of heat generated by the composite member in the cone calorimeter test can sufficiently be developed.
  • any suitable glass frit can be employed.
  • a glass frit is preferably a sinterable inorganic particle (glass frit), and more preferably an inorganic particle (glass frit) formed of at least one component selected from silicic acid (or silicon oxide), boric acid (or boron oxide), borosilicic acid, aluminum oxide, calcium oxide, sodium oxide, lithium oxide and phosphorus oxide.
  • Typical glass frits include phosphate glass frits, borosilicate glass frits, alkali-free glass frits and porcelain frits.
  • An especially preferable glass frit is a glass frit formed of at least a component containing phosphorus oxide.
  • the content of phosphorus oxide is, for example, 5 to 70 wt%; and the lower limit thereof is preferably 10 wt%, and more preferably 20 wt%; and the upper limit is preferably 60 wt%, and more preferably 50 wt%.
  • the effect of suppressing the amount of heat generated by the composite member in the cone calorimeter test can sufficiently be developed.
  • the average particle diameter of a glass frit is preferably 0.1 ⁇ m to 1,000 ⁇ m.
  • the lower limit of the average particle diameter of a glass frit is more preferably 0.5 ⁇ m, still more preferably 1 ⁇ m, and especially preferably 2 ⁇ m.
  • the upper limit of the average particle diameter of a glass frit is more preferably 500 ⁇ m, still more preferably 300 ⁇ m, and especially preferably 150 ⁇ m.
  • an inorganic particle having a hollow structure may be used as the inorganic particle (B).
  • examples of such an inorganic particle include silicas having a hollow structure, and glass frits (phosphate glass frits and the like) having a hollow structure (including hollow glass beads).
  • the upper limit is, for example, 500 ⁇ m, preferably 300 ⁇ m, more preferably 200 ⁇ m, and especially preferably 100 ⁇ m; and the lower limit is, for example, 1 nm.
  • the average particle diameter can be measured by a dynamic light scattering method or the like.
  • the content of an inorganic particle (B) in the silicone resin composition (C) is, for example, 0.1 to 500 parts by weight with respect to 100 parts by weight of the condensation-reactive silicone resin (A); the upper limit is preferably 400 parts by weight, and especially preferably 300 parts by weight; and the lower limit is preferably 0.5 parts by weight, more preferably 1 part by weight, and especially preferably 2 parts by weight.
  • a silicone resin composition containing the condensation-reactive silicone resin (A) and the inorganic particle (B) can be produced, for example, by adding the inorganic particle (B) to a silicone resin composition containing the condensation-reactive silicone resin (A) obtained by the above method.
  • additives such as a curing catalyst, as required, may be added to the silicone resin composition (C).
  • the upper limit is, for example, 95 wt%, and preferably 90 wt%; and the lower limit is, for example, 30 wt%, and preferably 40 wt%.
  • the flame-resistant composite member according to the present invention can be produced by providing a film (coated layer: flame-resistant silicone resin layer) formed of a silicone resin composition (C) containing at least the above-mentioned inorganic oxide particle-containing condensation-reactive silicone resin on at least one surface of a base material.
  • the flame-resistant composite member according to the present invention can be produced, for example, by forming a film by coating at least one surface of a base material with a silicone resin composition (C) containing at least the above inorganic oxide particle-containing condensation-reactive silicone resin.
  • a method for coating with the silicone resin composition (C) is not especially limited; and the silicone resin composition (C) is directly applied, for example, by a well-known coating method such as kiss coating, gravure coating, bar coating, spray coating, knife coating, wire coating, dip coating, die coating, curtain coating, dispenser coating, screen printing or metal mask printing, to thereby form a coated film;, and as required, for example, the film is dried at a temperature of about 80 to 150°C to thereby provide a flame-resistant composite member 3 having a film (coated layer) 2 comprising an inorganic oxide particle-containing silicone resin on one surface (or both surfaces) of a base material 1 as shown in Figure 1 .
  • a well-known coating method such as kiss coating, gravure coating, bar coating, spray coating, knife coating, wire coating, dip coating, die coating, curtain coating, dispenser coating, screen printing or metal mask printing
  • the flame-resistant composite member according to the present invention can also be produced by forming a film by coating a thin sheet body with a silicone resin composition (C) containing at least the above inorganic oxide particle-containing condensation-reactive silicone resin, and laminating the film on at least one surface of a base material.
  • a silicone resin composition (C) containing at least the above inorganic oxide particle-containing condensation-reactive silicone resin
  • the coating is preferably carried out by adding a water-soluble organic solvent excluding aliphatic monovalent alcohols to the silicone resin composition (C).
  • the amount of the water-soluble organic solvent excluding aliphatic monovalent alcohols used is not especially limited, but is, for example, 0.01 to 200 parts by weight, and preferably 0.1 to 150 parts by weight, with respect to 100 parts by weight of the silicone resin composition (C) (solid content).
  • water-soluble organic solvent excluding aliphatic monovalent alcohols include glycol ether-based solvents such as methyl cellosolve (2-methoxyethanol), ethyl cellosolve (2-ethoxyethanol), ethylene glycol isopropyl ether, butyl cellosolve, carbitol, butylcarbitol, diethylene glycol acetate, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, methoxymethoxyethanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether and ethylene glycol monoacetate, glycol-based solvents such as ethylene glycol, tetraethylene glycol, propylene glycol and dipropylene glycol, nitrogen-containing solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, and dimethyl sulfoxide.
  • glycol ether-based solvents such as methyl cellosolve (2-methoxyethanol), e
  • glycol ether-based solvents are preferable from the viewpoint of having a good solubility to hydrolyzed alkoxysilanes and condensates thereof.
  • the upper limit of the thickness of the film 2 is, for example, 1,000 ⁇ m, preferably 800 ⁇ m, and more preferably 500 ⁇ m; and the lower limit is, for example, 5 ⁇ m, preferably 10 ⁇ m, and more preferably 20 ⁇ m.
  • a protecting layer may be provided on the surface of the film formed of a silicone resin composition (C), and the main component of the protecting layer is preferably a polymer.
  • the protecting layer is preferably, for example, at least one selected from the group consisting of ultraviolet curing hard coat layers, thermosetting hard coat layers and organic-inorganic hybrid hard coat layers.
  • the protecting layer may be composed of only one layer or not less than two layers.
  • An ultraviolet curing hard coat layer can be formed from a resin composition containing an ultraviolet curing resin.
  • a thermosetting hard coat layer can be formed from a resin composition containing a thermosetting resin.
  • An organic-inorganic hybrid hard coat layer can be formed from a resin composition containing an organic-inorganic hybrid resin.
  • Curing compounds used for resins as described above more specifically include: monomers, oligomers and/or polymers having at least one selected from the group consisting of a silanol group, a precursor of a silanol group (for example, an alkoxysilyl group or a chlorosilyl group), an acryloyl group, a methacryloyl group, a cyclic ether group, an amino group and an isocyanate group; and silazane compounds.
  • a silanol group for example, an alkoxysilyl group or a chlorosilyl group
  • an acryloyl group for example, an alkoxysilyl group or a chlorosilyl group
  • acryloyl group for example, an alkoxysilyl group or a chlorosilyl group
  • a methacryloyl group a methacryloyl group
  • a cyclic ether group an amino group and an isocyanate group
  • the resin compositions can further contain any suitable additives according to the purpose.
  • suitable additives include photopolymerization initiators, silane coupling agents, mold release agents, curing agents, curing accelerators, diluents, antiaging agents, modifying agents, surfactants, dyes, pigments, discoloration preventing agents, ultraviolet absorbents, softening agents, stabilizers, plasticizers and defoaming agents.
  • the kinds, the number and the amounts of additives contained in the resin composition can suitably be set according to the purpose.
  • the thickness of the protecting layer is not especially limited, but is, for example, 0.1 to 200 ⁇ m, preferably 0.2 to 100 ⁇ m, and more preferably 0.5 to 50 ⁇ m. If the thickness of the protecting layer is in the above range, the excellent scratch resistance can be developed without impairing the flame resistance of the flame-resistant composite member according to the present invention.
  • the thickness of the flame-resistant composite member according to the present invention can suitably be selected according to applications, but the upper limit is usually 6,000 ⁇ m, preferably 5,000 ⁇ m, more preferably 4,000 ⁇ m, and still more preferably 3,000 ⁇ m; and the lower limit is, for example, 50 ⁇ m, preferably 90 ⁇ m, more preferably 120 ⁇ m, and especially preferably 170 ⁇ m.
  • the flame-resistant composite member according to the present invention has excellent flame resistance, and preferably has nonflammability.
  • the flame-resistant composite member hardly spreads fire or does not spread fire, for example, in a test according to the combustion test (for a general material: the 45° ethyl alcohol test of a railway rolling stock nonmetal material) of the Japan Railway Rolling Stock & Machinery Association.
  • the nonflammability means such a property that in the above combustion test, the surface of the member does not ignite or carbonize.
  • the flame-resistant composite member according to the present invention has excellent flame resistance, and preferably has a small amount of heat generated and a low heat generation rate.
  • the amount of heat generated and the maximum heat generation rate of the member can be reduced, and the ignition time can be retarded.
  • the total amount of heat generated per 10 min is not more than 30 MJ/m 2 ; the maximum heat generation rate is not more than 300 kW/m 2 ; and the ignition time is not less than 60 sec.
  • the flame-resistant composite member according to the present invention since being excellent in the flame resistance, can be utilized as interior members (transport machinery interior members) of transport machinery such as railway rolling stock, air carriers, automobiles, ships, elevators and escalators, building material members, display members, household appliance members and electronic circuit members.
  • the flame-resistant composite member can suitably be utilized also as illumination covers, particularly as illumination covers as transport machinery interior members.
  • the flame-resistant composite member according to the present invention can be used also as members deformed from plate-like materials by thermoforming.
  • a thermoforming method of plate-like materials can utilize well-known methods such as bending, press forming, vacuum forming and air pressure forming.
  • the flame-resistant composite member according to the present invention can be imparted with functional layers such as a hard coat layer, an antifouling layer, an antistatic layer, a light diffusion layer, an antireflection layer, an ultraviolet absorption layer, a heat barrier layer, a heat insulation layer, a heat transfer layer and a solvent resistant layer, in the range of not impairing the flame resistance.
  • functional layers such as a hard coat layer, an antifouling layer, an antistatic layer, a light diffusion layer, an antireflection layer, an ultraviolet absorption layer, a heat barrier layer, a heat insulation layer, a heat transfer layer and a solvent resistant layer, in the range of not impairing the flame resistance.
  • the flame-resistant composite member according to the present invention may contain any suitable other components in the base material and the film in the range of not impairing the flame resistance. One or not less than two of such other components may be contained.
  • the other components include other polymer components, softening agents, antioxidants, antiaging agents, curing agents, plasticizers, fillers, thermopolymerization initiators, photopolymerization initiators, ultraviolet absorbents, light stabilizers, colorants (pigments, dyes and the like), solvents (organic solvents), surfactants (for example, ionic surfactants, silicone-based surfactants and fluorine-based surfactants).
  • other polymer components softening agents, antioxidants, antiaging agents, curing agents, plasticizers, fillers, thermopolymerization initiators, photopolymerization initiators, ultraviolet absorbents, light stabilizers, colorants (pigments, dyes and the like), solvents (organic solvents), surfactants (for example, ionic surfactants, silicone-based surfactants and fluorine-based surfactants).
  • the illumination apparatus is an illumination apparatus using the above-mentioned flame-resistant composite member, and has, at least, a light source to generate light used for illumination, and an illumination cover installed so as to cover the light source and having the flame-resistant composite member, wherein light from the light source is transmitted through the flame-resistant composite member and emitted.
  • the fixation method of the illumination cover, the arrangement of the illumination cover, and the like are not especially limited, and well-known methods and arrangements can be employed.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 42 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a transparent resin composition solution B was obtained by using the similar experimental apparatus as in Synthesis Example 1 and by the similar process as in Synthesis Example 1, except for altering the amount of X-40-9225 to 67 g, the amount of 2-propanol to dissolve this to 67 g, the amount of X-40-9246 to 33 g, and the amount of 2-propanol to dissolve this to 33 g.
  • a transparent resin composition solution C was obtained by using the similar experimental apparatus as in Synthesis Example 1 and by the similar process as in Synthesis Example 1, except for altering the amount of X-40-9225 to 83 g, the amount of 2-propanol to dissolve this to 83 g, the amount of X-40-9246 to 17 g, and the amount of 2-propanol to dissolve this to 17 g.
  • a transparent resin composition solution D was obtained by using the similar experimental apparatus as in Synthesis Example 1 and by the similar process as in Synthesis Example 1, except for altering the amount of X-40-9225 to 92 g, the amount of 2-propanol to dissolve this to 92 g, the amount of X-40-9246 to 8 g, and the amount of 2-propanol to dissolve this to 8 g.
  • a transparent resin composition solution E was obtained by using the similar experimental apparatus as in Synthesis Example 1 and by the similar process as in Synthesis Example 1, except for altering the amount of X-40-9225 to 100 g, and the amount of 2-propanol to dissolve this to 100 g, and not adding X-40-9246 and 2-propanol to dissolve this.
  • the transparent resin composition solution A was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried in a hot air circulation-type oven at 90°C for 5 min, and thereafter dried at 120°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polypropylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polypropylene Plate PP-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polyethylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polyethylene Plate EL-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on an acryl plate (thickness: 2,000 ⁇ m, trade name: "Acrylite 001", made by Mitsubishi Rayon Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polystyrene plate (thickness: 2,000 ⁇ m, trade name: "PS", made by RP Topla Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polycarbonate sheet (thickness: 200 ⁇ m, trade name: “200KK ", made by Kaneka Corp.) so that the thickness after drying became 50 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried in a hot air circulation-type oven at 90°C for 3 min, and thereafter dried at 120°C for 15 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polypropylene sheet (thickness: 1,000 ⁇ m, trade name: "V37922", made by Okamoto Industries, Inc.) so that the thickness after drying became 50 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 30 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polypropylene sheet (thickness: 750 ⁇ m, trade name: "V37976", made by Okamoto Industries, Inc.) so that the thickness after drying became 50 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 30 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution A was applied on a polypropylene sheet (thickness: 500 ⁇ m, trade name: "V38241", made by Okamoto Industries, Inc.) so that the thickness after drying became 90 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried in a hot air circulation-type oven at 90°C for 30 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution B was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried in a hot air circulation-type oven at 90°C for 5 min, and thereafter dried at 120°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution C was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried in a hot air circulation-type oven at 90°C for 5 min, and thereafter dried at 120°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution D was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried in a hot air circulation-type oven at 90°C for 5 min, and thereafter dried at 120°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • the transparent resin composition solution E was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 45 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried in a hot air circulation-type oven at 90°C for 5 min, and thereafter dried at 120°C for 5 min to thereby obtain a formed body (flame-resistant composite member).
  • a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) as a single material was used for evaluation.
  • a polypropylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polypropylene Plate PP-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) as a single material was used for evaluation.
  • a polyethylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polyethylene Plate EL-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) as a single material was used for evaluation.
  • a polystyrene plate (thickness: 2,000 ⁇ m, trade name: "PS", made by RP Topla Ltd.) as a single material was used for evaluation.
  • a polycarbonate sheet (thickness: 200 ⁇ m, trade name: "200KK", made by Kaneka Corp.) as a single material was used for evaluation.
  • a polypropylene sheet (thickness: 1,000 ⁇ m, trade name: "V37922", made by Okamoto Industries, Inc.) as a single material was used for evaluation.
  • a polypropylene sheet (thickness: 750 ⁇ m, trade name: "V37976", made by Okamoto Industries, Inc.) as a single material was used for evaluation.
  • a polypropylene sheet (thickness: 500 ⁇ m, trade name: "V38241", made by Okamoto Industries, Inc.) as a single material was used for evaluation.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 42 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 84 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 126 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 42 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 84 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a silica particle (trade name: "AEROSIL R104", made by Nippon Aerosil Co., Ltd.) with respect to 100 parts by weight of the solid content in the transparent resin composition solution G obtained in Synthesis Example 7 was added to the transparent resin composition solution G, and stirred and mixed to thereby obtain a silicone resin composition D.
  • a silica particle (trade name: "AEROSIL R974", made by Nippon Aerosil Co., Ltd.) with respect to 100 parts by weight of the solid content in the transparent resin composition solution H obtained in Synthesis Example 8 was added to the transparent resin composition solution H, and stirred and mixed to thereby obtain a silicone resin composition G.
  • a magnesium hydroxide particle (trade name: "Kisuma 5A", made by Kyowa Chemical Industry Co., Ltd.) with respect to 100 parts by weight of the solid content in the transparent resin composition solution G obtained in Synthesis Example 7 was added to the transparent resin composition solution G, and stirred and mixed to thereby obtain a silicone resin composition Q.
  • the silicone resin composition A obtained in Example 14 was concentrated up to a solid content concentration of 76 wt%, and thereafter applied on a polypropylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polypropylene Plate PP-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) so that the thickness after drying became 90 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 30 min and at 120°C for 2 min to thereby obtain a flame-resistant composite member.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition B obtained in Example 15 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition C obtained in Example 16 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition D obtained in Example 17 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition E obtained in Example 18 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition F obtained in Example 19 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition G obtained in Example 20 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition D obtained in Example 17 in place of the silicone resin composition A obtained in Example 14, and using a polyethylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polyethylene Plate EL-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) in place of the polypropylene plate.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition E obtained in Example 18 in place of the silicone resin composition A obtained in Example 14, and using a polyethylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polyethylene Plate EL-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) in place of the polypropylene plate.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition H obtained in Example 21 in place of the silicone resin composition A obtained in Example 14.
  • a flame-resistant composite member was obtained by the similar operation as in Example 39, except for using the silicone resin composition I obtained in Example 22 in place of the silicone resin composition A obtained in Example 14.
  • the silicone resin composition J obtained in Example 23 was concentrated until the solid content concentration of the transparent resin composition solution therein became 76 wt%, and thereafter applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 200 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 30 min and at 120°C for 10 min to thereby obtain a flame-resistant composite member.
  • a polycarbonate plate thinness: 2,000 ⁇ m, trade name: "PC1600”, made by Takiron Co., Ltd.
  • a flame-resistant composite member was obtained by the similar operation as in Example 50, except for using the silicone resin composition K obtained in Example 24 in place of the silicone resin composition J obtained in Example 23.
  • a flame-resistant composite member was obtained by the similar operation as in Example 50, except for using the silicone resin composition L obtained in Example 25 in place of the silicone resin composition J obtained in Example 23.
  • a flame-resistant composite member was obtained by the similar operation as in Example 50, except for using the silicone resin composition M obtained in Example 26 in place of the silicone resin composition J obtained in Example 23.
  • a flame-resistant composite member was obtained by the similar operation as in Example 50, except for using the silicone resin composition N obtained in Example 27 in place of the silicone resin composition J obtained in Example 23.
  • a flame-resistant composite member was obtained by the similar operation as in Example 50, except for using the silicone resin composition O obtained in Example 28 in place of the silicone resin composition J obtained in Example 23.
  • the silicone resin composition P obtained in Example 29 was concentrated until the solid content concentration of the transparent resin composition solution therein became 76 wt%, and thereafter applied on a polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 200 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 30 min and at 120°C for 10 min to thereby obtain a flame-resistant composite member.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition Q obtained in Example 30 in place of the silicone resin composition P obtained in Example 29.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition R obtained in Example 31 in place of the silicone resin composition P obtained in Example 29.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition L obtained in Example 25 in place of the silicone resin composition P obtained in Example 29.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition L obtained in Example 25 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 240 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition L obtained in Example 25 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 350 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition S obtained in Example 32 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 300 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition T obtained in Example 33 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 300 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition T obtained in Example 33 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 400 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition U obtained in Example 34 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 300 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition U obtained in Example 34 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 500 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition V obtained in Example 35 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 400 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition W obtained in Example 36 in place of the silicone resin composition P obtained in Example 29.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition X obtained in Example 37 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 340 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 56, except for using the silicone resin composition Y obtained in Example 38 in place of the silicone resin composition P obtained in Example 29, and applying so that the thickness after drying became 340 ⁇ m.
  • the silicone resin composition L obtained in Example 25 was concentrated until the solid content concentration of the transparent resin composition solution therein became 76 wt%, and thereafter applied on a polycarbonate plate (thickness: 1,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 350 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 30 min and at 120°C for 10 min to thereby obtain a flame-resistant composite member.
  • a polycarbonate plate thinness: 1,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.
  • a flame-resistant composite member was obtained by the similar operation as in Example 71, except for using the silicone resin composition X obtained in Example 37 in place of the silicone resin composition L obtained in Example 25, and applying so that the thickness after drying became 360 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 71, except for using the silicone resin composition Y obtained in Example 38 in place of the silicone resin composition L obtained in Example 25, and applying so that the thickness after drying became 390 ⁇ m.
  • a polypropylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polypropylene Plate PP-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) as a single material was used for evaluation.
  • a polyethylene plate (thickness: 2,000 ⁇ m, trade name: "Kobe Polysheet Polyethylene Plate EL-N-AN", made by Shin-Kobe Electric Machinery Co., Ltd.) as a single material was used for evaluation.
  • a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) as a single material was used for evaluation.
  • a polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) as a single material was used for evaluation.
  • a polycarbonate plate (thickness: 1,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) as a single material was used for evaluation.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 83 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 83 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 83 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • a transparent resin composition solution 2-D was obtained by using the similar experimental apparatus as in Synthesis Example 2-1 and by the similar process as in Synthesis Example 2-2, except for altering the amount of the colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) to 75 g, and the amount of 2-propanol to dissolve this to 125 g.
  • the colloidal silica solution trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%
  • the silicone resin composition 2-A obtained in Example 2-1 was concentrated until the solid content concentration of the transparent resin composition solution therein became 75 wt%, and thereafter was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600”, made by Takiron Co., Ltd.), which had been subjected to a primer treatment with aminopropyltrimethoxysilane (trade name: "SILQUEST A-1110 SILANE", made by Momentive Performance Materials Inc.) by the similar method as in Primer Treatment Example 3-1 of a base material described later, so that the thickness after drying became 200 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 60 min, at 130°C for 15 min and at 170°C for 60 min to thereby obtain a flame-resistant composite member.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-11, except for using the silicone resin composition 2-B obtained in Example 2-2 in place of the silicone resin composition 2-A obtained in Example 2-1.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-11, except for using the silicone resin composition 2-C obtained in Example 2-3 in place of the silicone resin composition 2-A obtained in Example 2-1.
  • the silicone resin composition 2-D obtained in Example 2-4 was concentrated until the solid content concentration of the transparent resin composition solution therein became 75 wt%, and thereafter was applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600”, made by Takiron Co., Ltd.), which had been subjected to a primer treatment with aminopropyltrimethoxysilane (trade name: "SILQUEST A-1110 SILANE", made by Momentive Performance Materials Inc.) by the similar method as in Primer Treatment Example 3-1 of a base material described later, so that the thickness after drying became 370 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 40 min, at 130°C for 120 min and at 170°C for 5 min to thereby obtain a flame-resistant composite member.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-11, except for using the silicone resin composition 2-E obtained in Example 2-5 in place of the silicone resin composition 2-A obtained in Example 2-1, and applying so that the thickness after drying became 220 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-11, except for using the silicone resin composition 2-F obtained in Example 2-6 in place of the silicone resin composition 2-A obtained in Example 2-1, and applying so that the thickness after drying became 130 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-11, except for using the silicone resin composition 2-G obtained in Example 2-7 in place of the silicone resin composition 2-A obtained in Example 2-1, and applying so that the thickness after drying became 170 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-11, except for using the silicone resin composition 2-H obtained in Example 2-8 in place of the silicone resin composition 2-A obtained in Example 2-1.
  • the silicone resin composition 2-E obtained in Example 2-5 was concentrated until the solid content concentration of the transparent resin composition solution therein became 75 wt%, and thereafter was applied on a polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "Panlite Sheet PC-1151", made by Teijin Chemicals Ltd.), which had been subjected to a primer treatment with aminopropyltrimethoxysilane (trade name: "SILQUEST A-1110 SILANE”, made by Momentive Performance Materials Inc.) by the similar method as in Primer Treatment Example 3-1 of a base material described later, so that the thickness after drying became 230 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., thereafter dried under heating in a hot air circulation-type oven at 90°C for 60 min, at 130°C for 15 min and at 170°C for 60 min to thereby obtain a flame-resistant composite member.
  • a polycarbonate plate thinness: 1,500 ⁇ m, trade name: "Panlite Sheet PC-1151”,
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-19, except for using the silicone resin composition 2-I obtained in Example 2-12 in place of the silicone resin composition 2-E obtained in Example 2-5.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-19, except for using the silicone resin composition 2-J obtained in Example 2-13 in place of the silicone resin composition 2-E obtained in Example 2-5.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-19, except for applying so that the thickness after drying became 180 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-19, except for applying so that the thickness after drying became 300 ⁇ m.
  • a flame-resistant composite member was obtained by the similar operation as in Example 2-19, except for applying so that the thickness after drying became 250 ⁇ m, and using a polycarbonate plate (thickness: 1,200 ⁇ m, trade name: "Panlite Sheet PC-1151", made by Teijin Chemicals Ltd.) in place of the polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "Panlite Sheet PC-1151", made by Teijin Chemicals Ltd.).
  • a polycarbonate plate (thickness: 1,200 ⁇ m, trade name: "Panlite Sheet PC-1151", made by Teijin Chemicals Ltd.) as a single material was used for evaluation.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 84 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • 77 parts by weight of 2-propanol and 20 parts by weight of butanol were stirred and mixed with 3 parts by weight of a primer composition (trade name: "A-1110", made by Momentive Performance Materials Inc.) to thereby obtain a primer solution 3-A.
  • a primer composition trade name: "A-1110", made by Momentive Performance Materials Inc.
  • the primer solution 3-A was applied on a flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "N-7S", made by Mitsubishi Gas Chemical Co., Ltd.) so that the thickness after drying became 2 ⁇ m by using a Meyer bar, and thereafter dried under heating by a hot air circulation-type oven at 120°C for 120 min to thereby obtain a flame-resistant polycarbonate plate 3-A having been subjected to a primer treatment.
  • a flame-resistant polycarbonate plate 3-B was obtained by the similar operation as in Primer Treatment Example 3-1 of a base material, except for using a flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "NF-2000V", made by Mitsubishi Gas Chemical Co., Ltd.) in place of the flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "N-7S", made by Mitsubishi Gas Chemical Co., Ltd.).
  • a flame-resistant polycarbonate plate 3-C was obtained by the similar operation as in Primer Treatment Example 3-1 of a base material, except for using a flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "PZ-600", made by Takiron Co., Ltd.) in place of the flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "N-7S", made by Mitsubishi Gas Chemical Co., Ltd.).
  • the silicone resin composition 3-A obtained in Example 3-1 was concentrated until the solid content concentration of the transparent resin composition solution therein became 75 wt%, and thereafter applied on the primer-treated surface of the flame-resistant polycarbonate plate 3-A so that the thickness after drying became 350 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried under heating in a hot air circulation-type oven at 90°C for 60 min and at 130°C for 120 min to thereby obtain a flame-resistant composite member.
  • a flame-resistant composite member was obtained by the similar operation as in Example 3-2, except for using the flame-resistant polycarbonate plate 3-B in place of the flame-resistant polycarbonate plate 3-A.
  • a flame-resistant composite member was obtained by the similar operation as in Example 3-2, except for using the flame-resistant polycarbonate plate 3-C in place of the flame-resistant polycarbonate plate 3-A.
  • a flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "N-7S", made by Mitsubishi Gas Chemical Co., Ltd.) as a single material was used for evaluation.
  • a flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "NF-2000V", made by Mitsubishi Gas Chemical Co., Ltd.) as a single material was used for evaluation.
  • a flame-resistant polycarbonate plate (thickness: 1,500 ⁇ m, trade name: "PZ-600", made by Takiron Co., Ltd.) as a single material was used for evaluation.
  • a colloidal silica solution (trade name: Snowtex OS, made by Nissan Chemical Industries, Ltd., solid content concentration: 20%) having an average particle diameter of 8 to 11 nm, and 83 g of 2-propanol were added to a vessel equipped with a stirrer, a reflux cooler and a nitrogen introducing tube. A concentrated nitric acid was added thereto to regulate the acidity (pH) of the liquid in the range of 2 to 4.
  • the silicone resin composition 4-A obtained in Synthesis Example 4-2 was concentrated up to a solid content concentration of 75 wt%, and thereafter applied on a polycarbonate plate (thickness: 2,000 ⁇ m, trade name: "PC1600", made by Takiron Co., Ltd.) so that the thickness after drying became 450 ⁇ m by using an applicator made by Tester Sangyo Co., Ltd., and thereafter dried under heating in a hot air circulation-type oven at 90°C for 60 min, at 130°C for 15 min and at 170°C for 60 min to thereby obtain a flame-resistant composite member 4-A.
  • a mold-releasable silicone composite coating material (trade name: "Everhard No100", made by Ohashi Chemical Industries Ltd.) was applied on the flame-resistant composite member 4-A obtained in Synthesis Example 4-3 so that the thickness after drying became 50 ⁇ m, and dried at 130°C for 1 min to thereby obtain a scratch-resistant flame-resistant composite member 4-A.
  • a silicone hard coat agent (trade name: "KP-854", made by Shin-Etsu Chemical Co., Ltd.) was applied on the flame-resistant composite member 4-A obtained in Synthesis Example 4-3 so that the thickness after drying became 10 ⁇ m, and dried at 130°C for 1 min to thereby obtain a scratch-resistant flame-resistant composite member 4-B.
  • a combustion test was carried out according to the combustion test (for a general material: the 45° ethyl alcohol test of a railway rolling stock nonmetal material) of the Japan Railway Rolling Stock & Machinery Association by using a combustion test apparatus shown in Figure 2 .
  • reference numeral 11 denotes a test specimen (182 mm ⁇ 257 mm); reference numeral 12, an alcohol vessel (made of iron, 17.5 ⁇ ⁇ 7.1, 0.8t); and reference numeral 13, a vessel receiving platform (made of a cork or the like having a low heat conductivity).
  • the distance from the center of the test specimen lower surface to the vessel bottom surface was 25.4 mm (1 inch).
  • the flame-resistant composite member (in Comparative Examples, the plastic single material) fabricated in the above, as shown in Figure 2 , was held at an inclination of 45°; the fuel vessel (alcohol vessel) 12 was mounted on the platform (vessel receiving platform) 13 of a cork so that the center of the bottom of the fuel vessel 12 came at a position of 25.4 mm vertically under the center of the lower surface of the test specimen; and 0.5 cc of ethyl alcohol was put in the fuel vessel 12, and ignited, and left for about 2 min until the fuel burned up completely.
  • the presence/absence of ignition, carbonization, afterflame, penetration and melt dripping of the flame-resistant composite member (in Comparative Examples, the plastic single material) was visually observed, and evaluated according to the following criteria.
  • FIG. 3 A planar square-shaped test piece whose side was 100 mm was cut out, and, as shown in Figure 3 , was burned by irradiation for 10 min of heat rays of 50 kW/m 2 by using a cone calorimeter by a method according to ISO 5660-1:2002.
  • reference numeral 14 denotes an exhaust hood; reference numeral 15, a cone-type heater; reference numeral 16, a test specimen material; and reference numeral 17, a test specimen material holder.
  • the combustion determination was carried out using a total amount of heat generated (MJ/m 2 ), a maximum heat generation rate (kW/m 2 ) and an ignition time (sec) measured during the test time.
  • the scratch resistance of the scratch-resistant flame-resistant composite members of Examples was evaluated as follows.
  • a steel wool #0000 was uniformly attached on the smooth cross-section of a cylinder of 25 mm in diameter, and the cylinder was pressed on the surface of the flame-resistant composite member sample under the condition of a load of 400 g.
  • the cylinder having the steel wool attached thereon was set at about 100 mm per second in the velocity thereof, and reciprocated 10 times. Then, after the reciprocation, it was visually checked that no scratch of not less than 10 ⁇ m in width was generated on the surface of the sample, and the determination was carried out according to the following criteria.
  • C There were clearly scratches, and the visibility was impaired.
  • Example 40 Table 2 Railway Rolling Stock Material Combustion Test Combustion Test Cone Calorimeter Test Ignition/ Carbonization/ Afterflame Penetration/ Melt dripping Total Amount of Heat Generated (MJ/m 2 ) Maximum Heat Generation Rate (kW/m 2 ) Ignition Time (sec)
  • Example 40 Example 41 ⁇ Example 42 ⁇ Example 43 ⁇ Example 44 ⁇ Example 45 ⁇ Example 46 ⁇ Example 47 ⁇ Example 48 ⁇ Example 49 ⁇ Example 50 ⁇ ⁇ 37.4 ⁇ 432.0 ⁇ 143
  • Example 51 ⁇ ⁇ 37.9 ⁇ 388.0 ⁇ 131
  • Example 52 ⁇ ⁇ 38.7 ⁇ 308.0 ⁇ 104
  • Example 53 ⁇ ⁇ 44.2 ⁇ 524.9 ⁇ 102
  • Example 54 ⁇ ⁇ 41.9 ⁇ 452.0 ⁇ 126
  • Example 55 ⁇ 42.3 ⁇ 569.7 ⁇ 200
  • Example 56 ⁇ ⁇ 38.3 ⁇ 495.0 ⁇ 79
  • Table 5 Combustion Test Cone Calorimeter Test Scratch Resistance Ignition/ Carbonization/ Afterflame Penetration/ Melt dripping Total Amount of Heat Generated (MJ/m 2 ) Maximum Heat Generation Rate (kW/m 2 ) Ignition Time (sec)
  • Example 4-1 ⁇ ⁇ 20.1 ⁇ 248 ⁇ 115 A
  • Example 4-2 ⁇ ⁇ 20.8 ⁇ 291 ⁇ 114 A
  • the flame-resistant composite member according to the present invention since exhibiting remarkably high flame resistance even if having a flammable base material, is useful as illumination apparatuses, particularly illumination apparatuses requiring non-carbonization property, such as railway rolling stock applications.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Fireproofing Substances (AREA)
  • Silicon Polymers (AREA)
EP12850042.8A 2011-11-14 2012-11-13 Élément composé ignifuge Active EP2781350B1 (fr)

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JP2011249151 2011-11-14
JP2012090573 2012-04-11
JP2012248258A JP6088215B2 (ja) 2011-11-14 2012-11-12 難燃複合部材
PCT/JP2012/079346 WO2013073517A1 (fr) 2011-11-14 2012-11-13 Élément composé ignifuge

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CN103930272A (zh) 2014-07-16
US20140301090A1 (en) 2014-10-09
JP2013233789A (ja) 2013-11-21
EP2781350A4 (fr) 2015-08-05
CN103930272B (zh) 2016-09-14
US9707742B2 (en) 2017-07-18
EP2781350B1 (fr) 2020-10-28
WO2013073517A1 (fr) 2013-05-23

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